Thermochemistry

Nature of Energy even though Chemistry is the study of matter, energy effects matter energy is anything that has the capacity to do work work is a force acting over a distance Energy = Work = Force x Distance energy can be exchanged between objects through contact collisions Tro, Chemistry: A Molecular Approach

Classification of Energy Kinetic energy is energy of motion or energy that is being transferred thermal energy is kinetic Tro, Chemistry: A Molecular Approach

Classification of Energy Potential energy is energy that is stored in an object, or energy associated with the composition and position of the object energy stored in the structure of a compound is potential Tro, Chemistry: A Molecular Approach

Law of Conservation of Energy energy cannot be created or destroyed First Law of Thermodynamics energy can be transferred between objects energy can be transformed from one form to another heat → light → sound Tro, Chemistry: A Molecular Approach

Some Forms of Energy Electrical Heat or Thermal Energy kinetic energy associated with the flow of electrical charge Heat or Thermal Energy kinetic energy associated with molecular motion Light or Radiant Energy kinetic energy associated with energy transitions in an atom Nuclear potential energy in the nucleus of atoms Chemical potential energy in the attachment of atoms or because of their position Tro, Chemistry: A Molecular Approach

Units of Energy the amount of kinetic energy an object has is directly proportional to its mass and velocity KE = ½mv2 when the mass is in kg and speed in m/s, the unit for kinetic energy is 1 joule of energy is the amount of energy needed to move a 1 kg mass at a speed of 1 m/s 1 J = 1

Units of Energy joule (J) is the amount of energy needed to move a 1 kg mass a distance of 1 meter 1 J = 1 N∙m = 1 kg∙m2/s2 calorie (cal) is the amount of energy needed to raise one gram of water by 1°C kcal = energy needed to raise 1000 g of water 1°C food Calories = kcals Energy Conversion Factors 1 calorie (cal) = 4.184 joules (J) (exact) 1 Calorie (Cal) 1000 calories (cal) 1 kilowatt-hour (kWh) 3.60 x 106 joules (J) Tro, Chemistry: A Molecular Approach

Energy Use Unit Energy Required to Raise Temperature of 1 g of Water by 1°C Energy Required to Light 100-W Bulb for 1 hr Energy used to Run 1 Mile (approx) Energy Used by Average U.S. Citizen in 1 Day joule (J) 4.18 3.60 x 105 4.2 x 105 9.0 x 108 calorie (cal) 1.00 8.60 x 104 1.0 x 105 2.2 x 108 Calorie (Cal) 0.00100 86.0 100. 2.2 x 105 kWh 1.16 x 10-6 0.100 0.12 2.5 x 102 Tro, Chemistry: A Molecular Approach

Energy Flow and Conservation of Energy we define the system as the material or process we are studying the energy changes within we define the surroundings as everything else in the universe Conservation of Energy requires that the total energy change in the system and the surrounding must be zero DEnergyuniverse = 0 = DEnergysystem + DEnergysurroundings D is the symbol that is used to mean change final amount – initial amount

Energy Diagrams energy diagrams are a “graphical” way of showing the direction of energy flow during a process Internal Energy initial final energy added DE = + if the final condition has a larger amount of internal energy than the initial condition, the change in the internal energy will be + Internal Energy initial final if the final condition has a smaller amount of internal energy than the initial condition, the change in the internal energy will be ─ energy removed DE = ─ Tro, Chemistry: A Molecular Approach

─ DEsystem= DEsurroundings Energy Flow when energy flows out of a system, it must all flow into the surroundings when energy flows out of a system, DEsystem is ─ when energy flows into the surroundings, DEsurroundings is + therefore: ─ DEsystem= DEsurroundings Surroundings DE + System DE ─ Tro, Chemistry: A Molecular Approach

DEsystem= ─ DEsurroundings Energy Flow when energy flows into a system, it must all come from the surroundings when energy flows into a system, DEsystem is + when energy flows out of the surroundings, DEsurroundings is ─ therefore: DEsystem= ─ DEsurroundings Surroundings DE ─ System DE + Tro, Chemistry: A Molecular Approach

Energy Exchange energy is exchanged between the system and surroundings through either heat exchange or work being done Tro, Chemistry: A Molecular Approach

Heat & Work on a smooth table, most of the kinetic energy is transferred from the first ball to the second – with a small amount lost through friction Tro, Chemistry: A Molecular Approach

Heat & Work on a rough table, most of the kinetic energy of the first ball is lost through friction – less than half is transferred to the second Tro, Chemistry: A Molecular Approach

Heat Exchange heat is the exchange of thermal energy between the system and surroundings occurs when system and surroundings have a difference in temperature heat flows from matter with high temperature to matter with low temperature until both objects reach the same temperature thermal equilibrium Tro, Chemistry: A Molecular Approach

Quantity of Heat Energy Absorbed Heat Capacity when a system absorbs heat, its temperature increases the increase in temperature is directly proportional to the amount of heat absorbed the proportionality constant is called the heat capacity, C units of C are J/°C or J/K q = C x DT the heat capacity of an object depends on its mass 200 g of water requires twice as much heat to raise its temperature by 1°C than 100 g of water the heat capacity of an object depends on the type of material 1000 J of heat energy will raise the temperature of 100 g of sand 12°C, but only raise the temperature of 100 g of water by 2.4°C Tro, Chemistry: A Molecular Approach

Specific Heat Capacity measure of a substance’s intrinsic ability to absorb heat the specific heat capacity is the amount of heat energy required to raise the temperature of one gram of a substance 1°C Cs units are J/(g∙°C) the molar heat capacity is the amount of heat energy required to raise the temperature of one mole of a substance 1°C the rather high specific heat of water allows it to absorb a lot of heat energy without large increases in temperature keeping ocean shore communities and beaches cool in the summer allows it to be used as an effective coolant to absorb heat Tro, Chemistry: A Molecular Approach

Quantifying Heat Energy the heat capacity of an object is proportional to its mass and the specific heat of the material so we can calculate the quantity of heat absorbed by an object if we know the mass, the specific heat, and the temperature change of the object Heat = (mass) x (specific heat capacity) x (temp. change) q = (m) x (Cs) x (DT) Tro, Chemistry: A Molecular Approach

Example – How much heat is absorbed by a copper penny with mass 3 Example – How much heat is absorbed by a copper penny with mass 3.10 g whose temperature rises from -8.0°C to 37.0°C? T1= -8.0°C, T2= 37.0°C, m=3.10 g q, J q = m ∙ Cs ∙ DT Cs = 0.385 J/g (Table 6.4) Cs m, DT q

Bomb Calorimeter used to measure DE because it is a constant volume system Tro, Chemistry: A Molecular Approach

Example – When 1.010 g of sugar is burned in a bomb calorimeter, the temperature rises from 24.92°C to 28.33°C. If Ccal = 4.90 kJ/°C, find DE for burning 1 mole 1.010 g C12H22O11, T1 = 24.92°C, T2 = 28.33°C, Ccal = 4.90 kJ/°C DErxn, kJ/mol Ccal, DT qcal qcal qrxn qcal = Ccal x DT = -qrxn MM C12H22O11 = 342.3 g/mol

DHreaction = qreaction at constant pressure Enthalpy the enthalpy, H, of a system is the sum of the internal energy of the system and the product of pressure and volume H is a state function H = E + PV the enthalpy change, DH, of a reaction is the heat evolved in a reaction at constant pressure DHreaction = qreaction at constant pressure usually DH and DE are similar in value, the difference is largest for reactions that produce or use large quantities of gas Tro, Chemistry: A Molecular Approach

Endothermic and Exothermic Reactions when DH is ─, heat is being released by the system reactions that release heat are called exothermic reactions when DH is +, heat is being absorbed by the system reactions that absorb heat are called endothermic reactions chemical heat packs contain iron filings that are oxidized in an exothermic reaction ─ your hands get warm because the released heat of the reaction is absorbed by your hands chemical cold packs contain NH4NO3 that dissolves in water in an endothermic process ─ your hands get cold because they are giving away your heat to the reaction

Molecular View of Exothermic Reactions in an exothermic reaction, the temperature rises due to release of thermal energy this extra thermal energy comes from the conversion of some of the chemical potential energy in the reactants into kinetic energy in the form of heat during the course of a reaction, old bonds are broken and new bonds made the products of the reaction have less chemical potential energy than the reactants the difference in energy is released as heat

Molecular View of Endothermic Reactions in an endothermic reaction, the temperature drops due to absorption of thermal energy the required thermal energy comes from the surroundings during the course of a reaction, old bonds are broken and new bonds made the products of the reaction have more chemical potential energy than the reactants to acquire this extra energy, some of the thermal energy of the surroundings is converted into chemical potential energy stored in the products Tro, Chemistry: A Molecular Approach

C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(g) DH = -2044 kJ Enthalpy of Reaction the enthalpy change in a chemical reaction is an extensive property the more reactants you use, the larger the enthalpy change by convention, we calculate the enthalpy change for the number of moles of reactants in the reaction as written C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(g) DH = -2044 kJ DHreaction for 1 mol C3H8 = -2044 kJ DHreaction for 5 mol O2 = -2044 kJ Tro, Chemistry: A Molecular Approach

Example – How much heat is evolved in the complete combustion of 13 Example – How much heat is evolved in the complete combustion of 13.2 kg of C3H8(g)? 13.2 kg C3H8, q, kJ/mol 1 kg = 1000 g, 1 mol C3H8 = -2044 kJ, Molar Mass = 44.09 g/mol mol kJ kg g

Measuring DH Calorimetry at Constant Pressure reactions done in aqueous solution are at constant pressure open to the atmosphere the calorimeter is often nested foam cups containing the solution qreaction = ─ qsolution = ─(masssolution x Cs, solution x DT) DHreaction = qconstant pressure = qreaction to get DHreaction per mol, divide by the number of moles Tro, Chemistry: A Molecular Approach

Example – What is DHrxn/mol Mg for the reaction Mg(s) + 2 HCl(aq) → MgCl2(aq) + H2(g) if 0.158 g Mg reacts in 100.0 mL of solution to change the temperature from 25.6°C to 32.8°C? 0.158 g Mg, 100.0 mL sol’n, T1 = 25.6°C, T2 = 32.8°C, Cs = 4.18 J/°C, dsoln = 1.00 g/mL DHrxn, J/mol Mg qsoln = m x Cs x DT = -qrxn m, Cs, DT qsoln qsoln qrxn

Relationships Involving DHrxn when reaction is multiplied by a factor, DHrxn is multiplied by that factor because DHrxn is extensive C(s) + O2(g) → CO2(g) DH = -393.5 kJ 2 C(s) + 2 O2(g) → 2 CO2(g) DH = 2(-393.5 kJ) = 787.0 kJ if a reaction is reversed, then the sign of DH is reversed CO2(g) → C(s) + O2(g) DH = +393.5 kJ Tro, Chemistry: A Molecular Approach

Relationships Involving DHrxn Hess’s Law if a reaction can be expressed as a series of steps, then the DHrxn for the overall reaction is the sum of the heats of reaction for each step Tro, Chemistry: A Molecular Approach

Sample – Hess’s Law [3 NO2(g)  3 NO(g) + 1.5 O2(g)] DH° = (+259.5 kJ) Given the following information: 2 NO(g) + O2(g)  2 NO2(g) DH° = -173 kJ 2 N2(g) + 5 O2(g) + 2 H2O(l)  4 HNO3(aq) DH° = -255 kJ N2(g) + O2(g)  2 NO(g) DH° = +181 kJ Calculate the DH° for the reaction below: 3 NO2(g) + H2O(l)  2 HNO3(aq) + NO(g) DH° = ? [3 NO2(g)  3 NO(g) + 1.5 O2(g)] DH° = (+259.5 kJ) [1 N2(g) + 2.5 O2(g) + 1 H2O(l)  2 HNO3(aq)] DH° = (-128 kJ) [2 NO(g)  N2(g) + O2(g)] DH° = -181 kJ 3 NO2(g) + H2O(l)  2 HNO3(aq) + NO(g) DH° = - 49 kJ [2 NO2(g)  2 NO(g) + O2(g)] x 1.5 DH° = 1.5(+173 kJ) [2 N2(g) + 5 O2(g) + 2 H2O(l)  4 HNO3(aq)] x 0.5 DH° = 0.5(-255 kJ) [2 NO(g)  N2(g) + O2(g)] DH° = -181 kJ Tro, Chemistry: A Molecular Approach

Standard Conditions the standard state is the state of a material at a defined set of conditions pure gas at exactly 1 atm pressure pure solid or liquid in its most stable form at exactly 1 atm pressure and temperature of interest usually 25°C substance in a solution with concentration 1 M the standard enthalpy change, DH°, is the enthalpy change when all reactants and products are in their standard states the standard enthalpy of formation, DHf°, is the enthalpy change for the reaction forming 1 mole of a pure compound from its constituent elements the elements must be in their standard states the DHf° for a pure element in its standard state = 0 kJ/mol by definition Tro, Chemistry: A Molecular Approach

Formation Reactions reactions of elements in their standard state to form 1 mole of a pure compound if you are not sure what the standard state of an element is, find the form in Appendix IIB that has a DHf° = 0 since the definition requires 1 mole of compound be made, the coefficients of the reactants may be fractions Tro, Chemistry: A Molecular Approach

Writing Formation Reactions Write the formation reaction for CO(g) the formation reaction is the reaction between the elements in the compound, which are C and O C + O → CO(g) the elements must be in their standard state there are several forms of solid C, but the one with DHf° = 0 is graphite oxygen’s standard state is the diatomic gas C(s, graphite) + O2(g) → CO(g) the equation must be balanced, but the coefficient of the product compound must be 1 use whatever coefficient in front of the reactants is necessary to make the atoms on both sides equal without changing the product coefficient C(s, graphite) + ½ O2(g) → CO(g)

Calculating Standard Enthalpy Change for a Reaction any reaction can be written as the sum of formation reactions (or the reverse of formation reactions) for the reactants and products the DH° for the reaction is then the sum of the DHf° for the component reactions DH°reaction = S n DHf°(products) - S n DHf°(reactants) S means sum n is the coefficient of the reaction Tro, Chemistry: A Molecular Approach

The Combustion of CH4 Tro, Chemistry: A Molecular Approach

Sample - Calculate the Enthalpy Change in the Reaction 2 C2H2(g) + 5 O2(g) ® 4 CO2(g) + 2 H2O(l) 1. Write formation reactions for each compound and determine the DHf° for each 2 C(s, gr) + H2(g) ® C2H2(g) DHf° = +227.4 kJ/mol C(s, gr) + O2(g) ® CO2(g) DHf° = -393.5 kJ/mol H2(g) + ½ O2(g) ® H2O(l) DHf° = -285.8 kJ/mol Tro, Chemistry: A Molecular Approach

Sample - Calculate the Enthalpy Change in the Reaction 2 C2H2(g) + 5 O2(g) ® 4 CO2(g) + 2 H2O(l) 2. Arrange equations so they add up to desired reaction 2 C2H2(g) ® 4 C(s) + 2 H2(g) DH° = 2(-227.4) kJ 4 C(s) + 4 O2(g) ® 4CO2(g) DH° = 4(-393.5) kJ 2 H2(g) + O2(g) ® 2 H2O(l) DH° = 2(-285.8) kJ 2 C2H2(g) + 5 O2(g) ® 4 CO2(g) + 2 H2O(l) DH = -2600.4 kJ Tro, Chemistry: A Molecular Approach

DH°reaction = S n DHf°(products) - S n DHf°(reactants) Sample - Calculate the Enthalpy Change in the Reaction 2 C2H2(g) + 5 O2(g) ® 4 CO2(g) + 2 H2O(l) DH°reaction = S n DHf°(products) - S n DHf°(reactants) DHrxn = [(4•DHCO2 + 2•DHH2O) – (2•DHC2H2 + 5•DHO2)] DHrxn = [(4•(-393.5) + 2•(-285.8)) – (2•(+227.4) + 5•(0))] DHrxn = -2600.4 kJ Tro, Chemistry: A Molecular Approach

Example – How many kg of octane must be combusted to supply 1 Example – How many kg of octane must be combusted to supply 1.0 x 1011 kJ of energy? 1.0 x 1011 kJ mass octane, kg Write the balanced equation per mole of octane MMoctane = 114.2 g/mol, 1 kg = 1000 g DHf°’s DHrxn° kJ mol C8H18 g C8H18 kg C8H18 from above C8H18(l) + 25/2 O2(g) → 8 CO2(g) + 9 H2O(g) Material DHf°, kJ/mol C8H18(l) -250.1 O2(g) CO2(g) -393.5 H2O(g) -241.8 Look up the DHf° for each material in Appendix IIB